Cosmetic compositions containing block copolymers, tackifiers and a selective solvent for hard blocks

ABSTRACT

A cosmetic composition containing at least one block copolymer having at least one hard segment and at least one soft segment, at least one tackifier component, at least one solvent capable of solubilizing the at least one hard segment, and optionally, at least one colorant, and wherein the at least one hard segment has a T g  value of about 50° C. or more and the at least one soft segment has a T g  value of about 20° C. or less.

BACKGROUND OF THE INVENTION

There have been many developments in connection with improving comfort,wear, shine and/or longevity of cosmetic compositions for the face, eye,lips nails or hair. Commercially available lip treatment compositionssuch as lip glosses and lipsticks possess a certain level of gloss orshine depending of their composition. Efforts have been made through theuse of high refractive index fluids to further enhance the shine orgloss of such products, but the wear of gloss or shine is limited.Moreover, these lip treatment compositions are tacky and uncomfortableto apply due, oftentimes, to the presence of high molecular weightpolymers having a high viscosity which are used to maintain the wear ofshine/gloss.

While other efforts to improve shine/gloss involve the use of siliconefluids, wear of shine leaves much to be desired. Therefore, it is anobject of the present invention to provide a lip treatment compositionwhich is comfortable to apply and wear, and has long lastingshine/gloss.

BRIEF SUMMARY OF THE INVENTION

A first aspect of the present invention is directed to a cosmeticcomposition comprising:

-   -   (a) at least one block copolymer having at least one hard        segment and at least one soft segment;    -   (b) at least one tackifier component;    -   (c) at least one solvent capable of solubilizing the at least        one hard segment; and    -   (d) optionally, at least one colorant,    -   wherein the at least one hard segment has a T_(g) value of        50° C. or more, the at least one soft segment has a T_(g) value        of 20° C. or less.

A second aspect of the present invention is directed to a method oftreating lips by contacting the lips with the above-disclosed cosmeticcomposition.

DETAILED DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about”.

The physical and rheological properties of block copolymers can becontrolled by using specific types of solvents capable of solubilizingthe hard and/or soft block segments. A solvent capable of solubilizingthe soft segment causes the block copolymer to possess a morphology andrheology different from that obtained using a solvent capable ofsolubilizing the hard segment. Similarly, the physical properties of ablock copolymer solution based on a mixture of solvents capable ofsolubilizing both hard and soft segments are different from thoseobtained when using solvents capable of solubilizing only the softsegments or solvents capable of solubilizing only the hard segments.

It has been surprisingly discovered that a lip treatment compositioncontaining: (a) a block copolymer having at least one hard segment andat least one soft segment, (b) a tackifier, and (c) at least solventcapable of solubilizing the at least one hard segment of the blockcopolymer, can deliver a comfortable, long lasting shine or gloss whenapplied onto lips.

Block Copolymers

The block copolymers of the present invention are characterized by thepresence of at least one “hard” segment, and at least one “soft”segment. Aside from their compositional nature, the hard and softsegments of the block copolymers of the present invention are defined interms of their respective glass transition temperatures, “T_(g)” Moreparticularly, the hard segment has a T_(g) of 50° C. or more, whereasthe soft segment has a T_(g) of 20° C. or less. The glass transitiontemperature T_(g) for the hard block can range from 50° C. to 150° C.;60° C. to 125° C.; 70° C. to 120° C; 80° C. to 110° C. The glasstransition temperature T_(g) for the soft segment of the block copolymercan range from 20° C. to −150° C.; 0° C. to −135° C.; −10° C. to −125°C.; −25° C. to −100° C. A more in depth explanation can be found in U.S.Pat. Nos. 5,294,438 and 6,403,070, the entire contents of which arehereby incorporated by reference.

One type of block copolymer which may be employed by the presentinvention is a thermoplastic elastomer. The hard segments of thethermoplastic elastomer typically comprise vinyl monomers in varyingamounts. Examples of suitable vinyl monomers include, but are notlimited to, styrene, methacrylate, acrylate, vinyl ester, vinyl ether,vinyl acetate, and the like.

The soft segments of the thermoplastic elastomer comprise olefinpolymers and/or copolymers which may be saturated, unsaturated, orcombinations thereof. Suitable olefin copolymers may include, but arenot limited to, ethylene/propylene copolymers, ethylene/butylenecopolymers, propylene/butylene copolymers, polybutylene, polyisoprene,polymers of hydrogenated butanes and isoprenes, and mixtures thereof.

Thermoplastic elastomers useful in the present invention are blockcopolymers e.g., di-block, tri-block, multi-block, radial and star blockcopolymers, and mixtures and blends thereof. A di-block thermoplasticelastomer is usually defined as an A-B type or a hard segment (A)followed by a soft segment (B) in sequence. A tri-block is usuallydefined as an A-B-A type copolymer or a ratio of one hard, one soft, andone hard segment. Multi-block or radial block or star blockthermoplastic elastomers usually contain any combination of hard andsoft segments, provided that the elastomers possess both hard and softcharacteristics.

In some embodiments, the thermoplastic elastomer of the presentinvention may be chosen from the class of Kraton™ rubbers (ShellChemical Company) or from similar thermoplastic elastomers. Kraton™rubbers are thermoplastic elastomers in which the polymer chainscomprise a di-block, tri-block, multi-block or radial or star blockconfiguration or numerous mixtures thereof. The Kraton™ tri-blockrubbers have polystyrene (hard) segments on each end of a rubber (soft)segment, while the Kraton™ di-block rubbers have a polystyrene (hard)segment attached to a rubber (soft) segment. The Kraton™ radial or starconfiguration may be a four-point or other multipoint star made ofrubber with a polystyrene segment attached to each end of a rubbersegment. The configuration of each of the Kraton™ rubbers forms separatepolystyrene and rubber domains.

Each molecule of Kraton™ rubber is said to comprise block segments ofstyrene monomer units and rubber monomer and/or co-monomer units. Themost common structure for the Kraton™ triblock copolymer is the linearA-B-A block type styrene-butadiene-styrene, styrene-isoprene-styrene,styrene-ethylenepropylene-styrene, or styrene-ethylenebutylene-styrene.The Kraton™ di-block is preferably the AB block type such asstyrene-ethylenepropylene, styrene-ethylenebutylene, styrene-butadiene,or styrene-isoprene. The Kraton™ rubber configuration is well known inthe art and any block copolymer elastomer with a similar configurationis within the practice of the invention. Other block copolymers are soldunder the tradename Septon (which represent elastomers known as SEEPS,sold by Kurary, Co., Ltd) and those sold by Exxon Dow under thetradename Vector™.

Other thermoplastic elastomers useful in the present invention includethose block copolymer elastomers comprising astyrene-butylene/ethylene-styrene copolymer (tri-block), anethylene/propylene-styrene copolymer (radial or star block) or a mixtureor blend of the two. (Some manufacturers refer to block copolymers ashydrogenated block copolymers, e.g. hydrogenatedstyrene-butylene/ethylene-styrene copolymer (tri-block)).

The amounts of the block (co)polymer or (co)polymers, as well as theirstructure (di-block, tri-block, etc.), affect the nature of thethermoplastic elastomer, including its gelled form, which may range fromfragile to soft/flexible to firm. For instance, soft gels containrelatively high amounts of soft segments, and firm gels containrelatively high amounts of hard segments. The overall properties of thecomposition may also be affected by including more than one such blockcopolymer e.g., including a mixture of copolymers. For example, thepresence of tri-block copolymers enhances the integrity of the filmformed. The gel may also be transparent, translucent or opaque,depending upon the other cosmetically acceptable ingredients added, asdescribed herein.

It is preferred that the styrene content of the block copolymer be lessthan 30% by weight, preferably less than 25% by weight, and morepreferably less than 20% by weight, based on the weight of the blockcopolymer. This is because of the tendency of block copolymers having astyrene content of greater than 30% by weight to harden/gel inconventional carrier systems. However, in the event that a blockcopolymer having a styrene content of greater than 30% by weight isused, it may be necessary to also employ a co-solvent or functionalingredient capable of dissolving a styrene block in an amount effectiveto control the hardening/gelling of the styrene-containing elastomer inthe cosmetic composition.

A particularly preferred block copolymer for use in the presentinvention is a combination of di-block and tri-block copolymers ofstyrene-ethylene/butylene-styrene, commercially available from ShellChemical Company under trade name Kraton G1657M. It should be noted,however, that any thermoplastic elastomer of the block copolymer typehaving at least one soft and at least one hard segment may be usedwithout departing from the spirit of the invention.

The block copolymer is generally present in the cosmetic composition inan amount ranging from greater than 0% to 50% by weight; greater than 0%to 40% by weight; greater than 0% to 30% by weight; greater than 0% to20% by weight; greater than 0% to 10% by weight, based on the weight ofthe composition.

Tackifiers

A substance is described as a tackifier if, by adding it to a blockcopolymer, the resulting composition has the properties of a pressuresensitive adhesive. In general, tackifiers can be divided into fourdifferent families in terms of their chemistry: hydrocarbon resins,terpenes, amorphous (i.e. non-crystalline) rosins, rosin esters andtheir derivatives, and pure monomer resins. These tackifiers arecharacterized by their compatibility with at least one segment of theblock copolymer. By the term “compatible”, it is meant that when theblock copolymer and tackifier are mixed, the combination of at least onesegment of the block copolymer with the tackifier forms a polymer blendhaving a single glass transition temperature T_(g) which may be measuredby DMA, DSC or neutron light scattering.

The compatibility of the block copolymer and the tackifier may also bedefined in terms of solubility parameters. The solubility parameter δaccording to the Hansen solubility space is defined in the article“Solubility Parameter Values” by Eric A. Grulke in the work “PolymerHandbook” 3rd edition, Chapter VII, pages 519-559, the entire content ofwhich is hereby incorporated by reference, by the relationship:δ=(d _(D) ² +d _(P) ² +d _(H) ²)^(1/2), in which:

d_(D) characterizes the London dispersion forces resulting from theformation of dipoles induced during molecular impacts,

d_(P) characterizes the forces of Debye interactions between permanentdipoles,

d_(H) characterizes the forces of specific interactions (hydrogen bond,acid/base or donor/acceptor type and the like). The definition of thesolvents in the three-dimensional solubility space according to Hansenis given in the article by C. M. Hansen: “The three-dimensionalsolubility parameters” J. Paint Technol., 39, 105(1967), the entirecontent of which is hereby incorporated by reference.

The at least one tackifier used in the present invention will have asolubility parameter corresponding to an integer δ and the blockcopolymer will have at least one segment whose solubility parametercorresponds to δ±2, preferably δ±1.7, more preferably δ±1.5, morepreferably δ±1.3, more preferably δ±1.0, more preferably δ±0.7, morepreferably δ±0.5, and more preferably δ±0.3.

Examples of suitable tackifiers, include, but are not limited to,aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbonresins, hydrogenated polycyclopentadiene resins, polycyclopentadieneresins, gum rosins, gum rosin esters, wood rosins, wood rosin esters,tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modifiedpolyterpenes, terpene phenolics, aromatic modified hydrogenatedpolycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenatedaliphatic aromatic resins, hydrogenated terpenes and modified terpenes,hydrogenated rosin acids, hydrogenated rosin esters, polyisoprene,partially or fully hydrogenated polyisoprene, polybutenediene, partiallyor fully hydrogenated polybutenediene, and the like. As is evidenced bysome of the cited examples, the tackifier may be fully or partiallyhydrogenated. The tackifier may also be non-polar. (Non-polar meaningthat the tackifier is substantially free of monomers having polargroups. Preferably, the polar groups are not present, however, if theyare present, they are preferably present in an amount of up to about 5%by weight, preferably up to about 2% by weight, and more preferably upto about 0.5% by weight.)

In some embodiments, the tackifier may have a softening point (Ring andBall, as measured by ASTM E-28) of 80° C. to 150° C., preferably 100° C.to 130° C. In other embodiments the tackifier may be liquid and have anR and B softening point of between about −70° C. and 70° C.

In some embodiments, the tackifiers are hydrogenated hydrocarbon resinssuch as a hydrogenated styrene/methyl styrene/indene copolymer e.g.,styrene/methyl styrene/indene copolymers which include R1090, R1100,R7100, S1100, and S5100, all which are commercially available fromEastman Chemical under the trade name Regalite®. In other embodiments,aliphatic or aromatic hydrocarbon-based tackifying resins, for instancethe resins sold under the name “Piccotac” and “Hercotac” from Herculesor “Escorez” from Exxon, may also be used. It is also to be understoodthat mixtures of tackifiers may also be employed without departing fromthe spirit of the invention.

A particularly preferred tackifier for use in the present invention is ahydrogenated hydrocarbon resin such, for example, a hydrogenatedstyrene/methyl styrene/indene copolymer, commercially available fromEastman under the tradename Regalite® R1100.

The tackifier is present in the cosmetic composition of the presentinvention in an amount ranging from greater than 0% to 90% by weight;greater than 0% to 70% by weight; greater than 0% to 60% by weight;greater than 0% to 50% by weight; greater than 0% to 40%; greater than0% to 30% by weight; greater than 0% to 20% by weight, based on theweight of the composition.

Solvents

The cosmetic compositions of the present invention also contain at leastone solvent capable of solubilizing the at least one hard segment of theblock copolymer. Solvents which may be used herein are typicallycharacterized in terms of their viscosity at room temperature, weightaverage molecular weight and solubility parameter in relation to the atleast one hard segment of the block copolymer.

The solvent will have a viscosity, at room temperature, of from 1 to 200cps, preferably from 1 to 150 cps, more preferably from 1 to 100 cps,more preferably from 2 to 60 cps, and more preferably from 2 to 40 cps.

The solvent used in the present invention will have a solubilityparameter corresponding to an integer δ′ and the block copolymer willhave at least one hard segment whose solubility parameter corresponds toδ′±2, preferably δ′±1.7, more preferably δ′±1.5, more preferably δ′±1.3,more preferably δ′±1.0, more preferably δ′±0.7, more preferably δ′±0.5,and more preferably δ′±0.3.

Nonvolatile solvents which can be used in the invention include, but arenot limited to, monoesters, diesters, triesters, mixed aliphatic and/oraromatic, polar oils such as: hydrocarbon-based oils of animal origin,such as perhydrosqualene; hydrocarbon-based plant oils such as liquidtriglycerides of fatty acids and of glycerol, in which the fatty, acidsmay have varied chain lengths, these chains being linear or branched,and saturated or unsaturated; these oils can be chosen, for example,from wheat germ oil, sunflower oil, corn oil, soybean oil, marrow oil,grapeseed oil, blackcurrant seed oil, sesame oil, hazelnut oil, apricotoil, macadamia oil, castor oil, avocado oil, karite butter, sweet almondoil, cotton oil, alfalfa oil, poppy oil, pumpkin oil, evening primroseoil, millet oil, barley oil, quinoa oil, olive oil, rye oil, saffloweroil, candlenut oil, passion flower oil, musk rose oil andcaprylic/capric acid triglycerides such as those sold by the companyStearineries Dubois or those sold under the names Miglyol 810, 812 and818 by the company Dynamit Nobel; natural or synthetic esters of formulaR¹COOR², wherein R¹ is a higher fatty acid residue comprising 7 to 19carbon atoms, and R² is a branched hydrocarbon-based chain comprising 3to 20 carbon atoms, such as, for example, purcellin oil (cetostearyloctanoate), isopropyl myristate and alkyl or polyalkyl octanoates,decanoates or ricinoleates; synthetic ethers of formula R³COR⁴, whereinR³ is a C₃ to C₁₉ alkyl radical, and R⁴ is a C₃ to C₂₀ alkyl radical;fatty alcohols comprising at least 12 carbon atoms, such asoctyldodecanol or oleyl alcohol; cyclic hydrocarbons such as(alkyl)cycloalkanes, wherein the alkyl chain is linear or branched,saturated or unsaturated and comprises 1 to 30 carbon atoms, such ascyclohexane or dioctyl-cyclohexane; aromatic hydrocarbons, for example,alkenes such as benzene, toluene, 2,4-dimethyl-3-cyclohexene, dipentene,p-cymene, naphthalene or anthracene, and esters such as isostearylbenzoate; primary, secondary or tertiary amines such as triethanolamine;and mixtures thereof. In one embodiment, synthetic esters such asisopropyl myristate are used.

Preferred esters are those having a weight average molecular weight inthe range of 100 to 600, preferably from 100 to 500. Examples thereofinclude, but are not limited to, C12-15 alkyl benzoate, isopropylmyristate (Mw=270), isopropyl palmitate (Mw=300), isononyl isononanoate,cetyl ethylhexanoate (Mw=368), neopentyl glycol diethylhexanoate(Mw=356), diisopropyl sebacate (Mw=286).

The solvent capable of solubilizing the hard segment may typically bepresent in the composition of the invention in an amount of from greaterthan 0% to 85% by weight; greater than 0% to 75% by weight; greater than0% to 55% by weight; greater than 0% to 45% by weight; greater than 0%to 40% by weight, based on the weight of the composition.

According to a preferred embodiment of the present invention, thesolvent may be mixed with at least one co-solvent having a highmolecular weight and high viscosity, in order to improve the flow of thelip treatment composition during application onto the lips, as well asits feel and comfort thereon.

The high viscosity co-solvents have weight average molecular weightsranging from 500 to 4000, preferably from 500 to 3000, and morepreferably from 500 to 2500. Examples thereof include, but are notlimited to, capric/caprylic triglyceride (Mw=500), diisopropyl dimmerdilinoleate (Mw=644), diisostearyl fumarate (Mw=620), diisostearylmalate (Mw=640), pentaerythrityl tetraoleate, neopentyl glycoldiethylhexanoate, diethylhexyl sebacate and tricaprylate/tricaprate.

These co-solvents may be employed in the composition of the invention inan amount of from greater than 0% to 60% by weight; greater than 0% to50% by weight; greater than 0% to 40% by weight; greater than 0% to 30%by weight; greater than 0% to 25% by weight, all weights based on theweight of the composition.

In the event that at least one hard segment solvent, and at least onehard segment co-solvent are used in combination, the mixture will have aviscosity of from 20 to 5000 cps, preferably from 20 to 2000 cps, andmore preferably from 20 to 1500 cps. The viscosity of the mixture isdetermined using the formula:$\eta_{mix} = {\prod\limits_{i}^{n}\quad\eta_{i}^{\phi_{i}}}$wherein η_(mix) represents the viscosity of the mixture, η_(i)represents the viscosity of the individual components, and φ_(i)represents the weight fraction of the individual components.

Colorant

The cosmetic compositions of the present invention may also contain atleast one cosmetically acceptable colorant such as a pigment ordyestuff. Examples of suitable pigments include, but are not limited to,inorganic pigments, organic pigments, lakes, pearlescent pigments,irridescent or optically variable pigments, and mixtures thereof. Apigment should be understood to mean inorganic or organic, white orcolored particles. Said pigments may optionally be surface-treatedwithin the scope of the present invention but are not limited totreatments such as silicones, perfluorinated compounds, lecithin, andamino acids.

Representative examples of inorganic pigments useful in the presentinvention include those selected from the group consisting of rutile oranatase titanium dioxide, coded in the Color Index under the referenceCI 77,891; black, yellow, red and brown iron oxides, coded underreferences CI 77,499, 77,492 and, 77,491; manganese violet (CI 77,742);ultramarine blue (CI 77,007); chromium oxide (CI 77,288); chromiumhydrate (CI 77,289); and ferric blue (CI 77,510) and mixtures thereof.

Representative examples of organic pigments and lakes useful in thepresent invention include, but are not limited to, D&C Red No. 19 (CI45,170), D&C Red No. 9 (CI 15,585), D&C Red No. 21 (CI 45,380), D&COrange No. 4 (CI 15,510), D&C Orange No. 5 (CI 45,370), D&C Red No. 27(CI 45,410), D&C Red No. 13 (CI 15,630), D&C Red No. 7 (CI 15,850), D&CRed No. 6 (CI 15,850), D&C Yellow No. 5 (CI 19,140), D&C Red No. 36 (CI12,085), D&C Orange No. 10 (CI 45,425), D&C Yellow No. 6 (CI 15,985),D&C Red No. 30 (CI 73,360), D&C Red No.3 (CI 45,430) and the dye orlakes based on Cochineal Carmine (CI 75,570) and mixtures thereof.

Representative examples of pearlescent pigments useful in the presentinvention include those selected from the group consisting of the whitepearlescent pigments such as mica coated with titanium oxide, micacoated with titanium dioxide, bismuth oxychloride, titanium oxychloride,colored pearlescent pigments such as titanium mica with iron oxides,titanium mica with ferric blue, chromium oxide and the like, titaniummica with an organic pigment of the above-mentioned type as well asthose based on bismuth oxychloride and mixtures thereof.

The precise amount and type of colorant employed in the compositions ofthe present invention will depend on the color, intensity and use of thecosmetic composition and, as a result, will be determined by thoseskilled in the art of cosmetic formulation.

Shine Enhancing Agents

It may, at times, be desirable to provide cosmetic compositions havingenhanced shine/gloss properties. In those instances, at least one shineenhancing agent would be employed in the composition.

Suitable shine enhancing agents include those compounds having arefractive index ranging from 1.45 to 1.60, and a weight averagemolecular weight of less than 15,000, preferably less than 10,000,preferably less than 2,000. Examples thereof include, but are notlimited to, phenylated silicones such as those commercialized under thetrade name “Abil AV 8853” by Goldschmidt, those commercialized under thetrade names “DC 554”, “DC 555”, “DC 556”, ISF 558” by Dow Corning; andthose commercialized under the trade name “Silbione 70633 V 30” byRhône-Poulenc.

Additional examples of suitable phenylated silicones include, but arenot limited to, those commercialized by Wacker Silicones such as BelsilPDM 20, a phenylated silicone with a viscosity at 250C. of approximately20 cSt; Belsil PDM 200, a phenylated silicone with a viscosity at 25° C.of approximately 200 cSt; Belsil PDM 1000, a phenylated silicone with aviscosity at 25° C. of approximately 1000 cSt.

Additional examples of suitable shine enhancing agents include, but arenot limited to, polycyclopentadiene, poly(propylene glycol) dibenzoate(n_(D)=1.5345), aminopropyl phenyl trimethicone (n_(D)=1.49-1.51),pentaerythrityl tetraoleate commercially available as Puresyn 4E68(n_(D)=1.473) from ExxonMobil, and PPG-3 benzyl ether myristatecommercially available as Crodamol STS (n_(D)=1.4696) from Croda Inc.

Particularly preferred shine enhancing agents are the phenylatedsilicones such as phenyl trimethicone, and trimethyl pentaphenyltrisiloxane, and esters such as pentaerythrityl tetraoleate, and PPG-3benzyl ether myristate.

The shine enhancing agent may be present in the composition of theinvention in an amount of up to 40% by weight; up to 30% by weight; upto 20% by weight; from 1 to 20% by weight; from 2 to 20% by weight,based on the weight of the composition.

Modified Silicones

The cosmetic compositions of the present invention may contain at leastone modified silicone to improve the texture and comfort. Examples ofsuitable modified silicones include, but are not limited to,polyethyleneoxy- and/or polypropyleneoxy-modified silicone,alkoxy-modified silicone, hydroxyalkyl-modified silicone,acyloxyalkyl-modified silicone, alkyl-modified silicone, amino-modifiedsilicone, epoxy-modified silicone, carboxyl-modified silicone,chloroalkyl-modified silicone, alkyl-higher-alcohol-ester-modifiedsilicone, alcohol-modified silicone, polyether-modified silicone,phenyl-modified silicone, alkylpolyglyceryl-modified silicone,perfluoroalkyl polyether-co-modified silicone and fluorine-modifiedsilicone.

The modified silicone may be present in the composition of the inventionin an amount of up to 30% by weight; up to 25% by weight; up to 20% byweight; up to 10% by weight; up to 8% by weight, based on the weight ofthe composition.

Waxes

In some embodiments, it may be desirable to formulate cosmeticcompositions in accordance with the present invention which are free ofwax. However, in the event that a wax is employed, it will be present inan amount of from about 0.1% to about 30% by weight, based on the totalweight of the composition. Suitable waxes are those generally used incosmetics and dermatology. Examples thereof include, but are not limitedto, those of natural origin such as beeswax, carnauba wax, candelillawax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffinwax, lignite wax, microcrystalline waxes, lanolin wax, montan wax,ozokerites and hydrogenated oils such as hydrogenated jojoba oil.Examples of suitable synthetic waxes include, but are not limited to,polyethylene waxes derived from the polymerization of ethylene, waxesobtained by Fischer-Tropsch synthesis, fatty acid esters and glyceridesthat are solid at 40° C., for example, at above 55° C., silicone waxessuch as alkyl- and alkoxy-poly(di)methylsiloxanes and/orpoly(di)methyl-siloxane esters that are solid at 40° C., for example, atabove 55° C.

Gelling Agents

The compositions of the invention may also be optionally gelled with anoil-phase gelling agent. The gelling agent increases the liquid fattyphase viscosity and leads to a solid or flowable composition whenintroduced in said fatty phase. The gelling agent does not encompasswaxes, in the sense that it is not waxy. The at least one gelling agentmay be chosen from gelling agents in polymeric form and gelling agentsin mineral form. The gelling agent may be chosen from agents that gelvia chemical reticulation and agents that gel via physical reticulation.

Modified clays may be used as gelling agents, examples of which include,but are not limited to, hectorites modified with an ammonium chloride ofa C₁₀ to C₂₂ fatty acid, such as hectorite modified withdistearyldimethylammonium chloride, also known as quaternium-18bentonite, such as the products sold or made under the names Bentone 34by the company Rheox, Claytone XL, Claytone 34 and Claytone 40 sold ormade by the company Southern Clay, the modified clays known under thename quaternium-18 benzalkonium bentonites and sold or made under thenames Claytone HT, Claytone GR and Claytone PS by the company SouthernClay, the clays modified with stearyldimethylbenzoylammonium chloride,known as stearalkonium bentonites, such as the products sold or madeunder the names Claytone APA and Claytone AF by the company SouthernClay, and Baragel 24 sold or made by the company Rheox.

Other mineral gelling agents, which can be used in the invention,include silica, such as fumed silica. The fumed silica may have aparticle size, which may be nanometric to micrometric, for exampleranging from 5 nm to 200 nm.

The fumed silicas may be obtained by high-temperature hydrolysis of avolatile silicon compound in a hydrogen-oxygen flame, producing a finelydivided silica. This process makes it possible to obtain hydrophilicsilicas that have a large number of silanol groups at their surface.Such hydrophilic silicas are sold or made, for example, under the names“Aerosil 130®”, “Aerosil 200®”, “Aerosil 255®”, “Aerosil 300®” and“Aerosil 380®” by the company Degussa, and “CAB-O-SIL HS-5®”, “CAB-O-SILEH-5®”, “CAB-O-SIL LM-130®”, “CAB-O-SIL MS-55®” and “CAB-O-SIL M-5®” bythe company Cabot.

It is thus possible to chemically modify the surface of the hydrophilicsilica by chemical reaction, producing a reduction in the number ofsilanol groups. The silanol groups can be replaced, for example, withhydrophobic groups: this then gives a hydrophobic silica. Thehydrophobic groups may be: trimethylsiloxyl groups, which are obtainedin particular by treating fumed silica in the presence ofhexamethyldisilazane. Silicas thus treated are known as “silicasilylate” according to the CTFA dictionary (6th edition, 1995). They aresold or made, for example, under the references “Aerosil R812®” by thecompany Degussa and “CAB-O-SIL TS-530®” by the company Cabot;dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained inparticular by treating fumed silica in the presence ofpolydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated areknown as “silica dimethyl silylate” according to the CTFA dictionary(6th edition, 1995). They are sold or made, for example, under thereferences “Aerosil R972®” and “Aerosil R974®” by the company Degussa,and “CAB-O-SIL TS-610®” and “CAB-O-SIL TS-720®” by the company Cabot;groups derived from reacting fumed silica with silane alkoxides orsiloxanes. These treated silicas are, for example, the products sold ormade under the reference “Aerosil R805®” by the company Degussa.

According to the invention, hydrophobic silica, such as fumed silica,may be used as a lipophilic gelling agent. The use of fumed silica makesit possible to obtain a translucent or even transparent composition, inparticular in the form of a stick, which does not exude, in the absenceof opacifying particles such as waxes, fillers and pigments (includingnacres).

The at least one lipophilic gelling agent can allow the exudation of thecomposition to be limited and can allow its stability to be increased,while at the same time conserving the composition's glossy appearance,which is not possible with waxes such as those used conventionally incosmetics and dermatology.

The at least one gelling agent, if used, will typically be present in anamount of from 0.1% to 20% by weight, preferably from 0.1% to 15% byweight, and more preferably from 0.1 to 10% by weight, based on theweight of the composition.

Additives/Auxiliary Agents

The compositions of the present invention may further comprise at leastone cosmetically or dermatologically acceptable additive such as athickener, a film former, a plasticizer, an antioxidant, an essentialoil, a preserving agent, a fragrance, a filler, a pasty fatty substance,a waxy fatty substance, a neutralizing agent, and a polymer, andcosmetically active agents and/or dermatological active agents such as,for example, emollients, moisturizers, vitamins, essential fatty acidsand medicaments.

While the use of a plasticizer is not necessary in the lip treatmentcompositions of the present invention, its use may, nevertheless, bedesirable. Plasticizers are organic compounds added to a high polymerboth to facilitate processing and to increase the flexibility andtoughness of the final product by internal modification of the polymermolecule. Examples of suitable plasticizers include, but are not limitedto, oils, cellulose esters, phthalate esters, adipate esters, sebacateesters, tricresyl phosphate, castor oil, glycol ethers, benzyl alcohol,triethyl citrate, and propylene carbonate.

Particularly preferred plasticizers include isopropyl palmitate andalkyl benzoate. A plasticizer, if used, will typically be present in anamount of from 1 to 70% by weight, preferably from 2 to 50% by weight,and more preferably from 5 to 20% by weight, based on the weight of thecomposition.

Representative examples of preservatives include alkylpara-hydroxybenzoates, wherein the alkyl radical has from 1, 2, 3, 4, 5or 6 carbon atoms and preferably from 1 to 4 carbon atoms e.g., methylpara-hydroxybenzoate (methylparaben), ethyl para-hydroxybenzoate(ethylparaben), propyl para-hydroxybenzoate (propylparaben), butylpara-hydroxybenzoate (butylparaben) and isobutyl para-hydroxybenzoate(isobutylparaben). Mixtures of preservatives may certainly be used,e.g., the mixture of methyl-paraben, ethylparaben, propylparaben andbutylparaben sold under the name Nipastat by Nipa, and the mixture ofphenoxyethanol, methylparaben, ethylparaben, propylparaben andbutylparaben sold under the name Phenonip, also by Nipa. Thesepreservatives may be present in amounts ranging from about 0.01 to about10% by weight, preferably from 0.5% to about 5% by weight, and morepreferably from about 0.8 to about 3% by weight, based on the weight ofthe composition.

Fillers that may be used in the compositions of the invention include,for example, silica powder; talc; polyamide particles and especiallythose sold under the name Orgasol by the company Atochem; polyethylenepowders; microspheres based on acrylic copolymers, such as those basedon ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold bythe company Dow Corning under the name Polytrap; expanded powders suchas hollow microspheres and especially the microspheres sold under thename Expancel by the company Kemanord Plast or under the name MicropearlF 80 ED by the company Matsumoto; powders of natural organic materialssuch as crosslinked or noncrosslinked corn starch, wheat starch or ricestarch, such as the powders of starch crosslinked with octenyl succinateanhydride, sold under the name Dry-Flo by the company National Starch;silicone resin microbeads such as those sold under the name Tospearl bythe company Toshiba Silicone; clays (bentone, laponite, saponite, etc.)and mixtures thereof. These fillers may be present in amounts rangingfrom about 0.1 to about 50% by weight, preferably from 0.5 to about 30%by weight, and more preferably from about 1 to about 20% by weight,based on the weight of the composition.

The compositions of the present invention may further comprise a safeand effective amount of at least one active ingredient orpharmaceutically acceptable salt thereof. The term “safe and effectiveamount” as used herein, means an amount sufficient to modify thecondition to be treated or to deliver the desired skin benefit, while atthe same time avoiding serious side effects, at a reasonable benefit torisk ratio within the scope of sound medical judgment. What is a safeand effective amount of the active ingredient will vary with thespecific active agent, the ability of the active agent to penetratethrough the skin, the age, health and skin condition of the user, andother like factors. Typically, the active ingredient may be present inamounts ranging from about 0.01 to about 20% by weight, preferably from0.1 to about 10% by weight, and more preferably from about 0.5 to about5% by weight, based on the weight of the composition.

The active ingredients useful herein can be categorized by theirtherapeutic benefit or their postulated mode of action. However, it isto be understood that the active ingredients useful herein can in someinstances provide more than one therapeutic benefit or operate via morethan one mode of action. Therefore, classifications herein are made forthe sake of convenience and are not intended to limit the activeingredient to that particular application or applications listed. Also,pharmaceutically acceptable salts of these active ingredients are usefulherein. The following active ingredients are useful in the compositionsof the present invention.

Anti-Acne Actives: Examples of useful anti-acne actives include thekeratolytics such as salicylic acid (o-hydroxybenzoic acid), derivativesof salicylic acid such as 5-octanoyl salicylic acid, and resorcinol;retinoids such as retinoic acid and its derivatives (e.g., cis andtrans); sulfur-containing D and L amino acids and their derivatives andsalts, particularly their N-acetyl derivatives, a preferred example ofwhich is N-acetyl-L-cysteine; lipoic acid; antibiotics andantimicrobials such as benzoyl peroxide, octopirox, tetracycline,2,4,4′-trichloro-2′-hydroxy diphenyl ether, 3,4,4′-trichlorobanilide,azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol,phenoxyisopropanol, ethyl acetate, clindamycin and meclocycline;sebostats such as flavonoids; and bile salts such as scymnol sulfate andits derivatives, deoxycholate, and cholate.

Antimicrobial and Antifungal Actives: Examples of antimicrobial andantifungal actives include .beta.-lactam drugs, quinolone drugs,ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin,2,4,4′-trichloro-2′-hydroxy diphenyl ether, 3,4,4′-trichlorobanilide,phenoxyethanol, phenoxy propanol, phenoxyisopropanol, doxycycline,capreomycin, chlorhexidine, chlortetracycline, oxytetracycline,clindamycin, ethambutol, hexamidine isethionate, metronidazole,pentamidine, gentamicin, kanamycin, lineomycin, methacycline,methenamine, minocycline, neomycin, netilmicin, paromomycin,streptomycin, tobramycin, miconazole, tetracycline hydrochloride,erythromycin, zinc erythromycin, erythromycin estolate, erythromycinstearate, amikacin sulfate, doxycycline hydrochloride, capreomycinsulfate, chlorhexidine gluconate, chlorhexidine hydrochloride,chlortetracycline hydrochloride, oxytetracycline hydrochloride,clindamycin hydrochloride, ethambutol hydrochloride, metronidazolehydrochloride, pentamidine hydrochloride, gentamicin sulfate, kanamycinsulfate, lineomycin hydrochloride, methacycline hydrochloride,methenamine hippurate, methenamine mandelate, minocycline hydrochloride,neomycin sulfate, netilmicin sulfate, paromomycin sulfate, streptomycinsulfate, tobramycin sulfate, miconazole hydrochloride, amanfadinehydrochloride, amanfadine sulfate, octopirox, parachlorometa xylenol,nystatin, tolnaftate and clotrimazole.

The cosmetic compositions of this invention may also contain sunscreens,which are chemical absorbers that actually absorb harmful ultravioletradiation. It is well known that chemical absorbers are classified,depending on the type of radiation they protect against, as either UV-Aor UV-B absorbers. UV-A absorbers generally absorb radiation in the 320to 400 nm region of the ultraviolet spectrum. UV-A absorbers includeanthranilates, benzophenones, and dibenzoyl methanes. UV-B absorbersgenerally absorb radiation in the 280 to 320 nm region of theultraviolet spectrum. UV-B absorbers include p-aminobenzoic acidderivatives, camphor derivatives, cinnamates, and salicylates.

The sunscreens useful in the present invention typically comprisechemical absorbers, but may also comprise physical blockers. Exemplarysunscreens which may be formulated into the compositions of the presentinvention are chemical absorbers such as p-aminobenzoic acidderivatives, anthranilates, benzophenones, camphor derivatives, cinnamicderivatives, dibenzoyl methanes (such as avobenzone also known asParsol® 1789), diphenylacrylate derivatives, salicylic derivatives,triazine derivatives, benzimidazole compounds, bis-benzoazolylderivatives, methylene bis-(hydroxyphenylbenzotriazole) compounds, thesunscreen polymers and silicones, or mixtures thereof. Also exemplary ofthe sunscreens which may be formulated into the compositions of thisinvention are physical blockers such as cerium oxides, chromium oxides,cobalt oxides, iron oxides, red petrolatum, silicone-treated titaniumdioxide, titanium dioxide, zinc oxide, and/or zirconium oxide, ormixtures thereof.

Examples of suitable sunscreens include, but are not limited to:aminobenzoic acid, amyldimethyl PABA, cinoxate, diethanolaminep-methoxycinnamate, digalloyl trioleate, dioxybenzone, 2-ethoxyethylp-methoxycinnamate, ethyl 4-bis(hydroxypropyl)aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethylhexylp-methoxycinnamate, 2-ethylhexyl salicylate, glyceryl aminobenzoate,homomenthyl salicylate, homosalate, 3-imidazol-4-ylacrylic acid andethyl ester, methyl anthranilate, octyldimethyl PABA,2-phenylbenzimidazole-5-sulfonic acid and salts, red petrolatum,sulisobenzone, titanium dioxide, triethanolamine salicylate,N,N,N-trimethyl-4-(2-oxoborn-3-ylidene methyl)anillinium methyl sulfate,and mixtures thereof.

The lip treatment composition of the invention may be in the form of alipstick, a lip gloss or a lip pencil, optionally having care ortreating properties.

Rheology

The rheological properties of lip-gloss compositions in accordance withthe present invention are determined by using a controlled stressrheometer, commercially available from TA Instruments under the nameAR-G2. The samples are measured using a parallel plate having astainless steel, cross hatched, 40 mm diameter plate. The gap is set at1,000 microns. The desired temperature is precisely controlled by aPeltier system.

The lip-gloss sample is transferred to the rheometer, and heated to 35°C. for about 10 minutes. The sample is then cooled and held at 25° C.for about 10 minutes or more.

The linear viscoelastic regime is determined by oscillation stress sweepmode with a range of from 1 mN.m to 100 mN.m, at a constant frequency of1 rad/s. Said linear viscoelastic regime corresponds to theelastic/storage modulus G′, within the above range, when theelastic/storage modulus G′ is constant, or nearly constant, at theapplied oscillation stress.

The frequency sweep experiment is then performed from 100 rad/s to 0.01rad/s at a low oscillation stress in the linear viscoelastic regime. Theelastic/storage modulus G′ at a frequency ω of 0.01 rad/s is determinedfrom the frequency sweep mode.

The lower the value of the elastic/storage modulus G′, at a frequency ωof 0.01 rad/s, the better the wetting property and the less creepresistance for the lip-gloss composition.

In the linear viscoelastic regime, the elastic/storage modulus G′ at afrequency ω of 0.01 rad/s, of compositions in accordance with thepresent invention, is in the range of from 0.01 Pa to 500 Pa at 25° C.

After finishing the dynamic oscillation experiment, the same sample isequilibrated for 10 minutes, at a constant temperature of 25° C. Creepand recovery measurements are then performed at a constant stress of 0.8Pa.

The creep viscosity (η_(creep)) of the lip gloss composition, measuredat a constant stress (σ) of 0.8 Pa, is determined from the creep strain(γ_(creep)) and the recoverable strain (γ_(recovery)), wherein the creepstrain duration (t_(creep)) is 10 minutes and the recoverable strainduration is 30 minutes. The creep viscosity is calculated by thefollowing expression:$\eta_{creep} = \frac{\sigma\quad t_{creep}}{\left( {{\gamma_{creep}\left( {t = {10\quad\min}} \right)} - {\gamma_{recovery}\left( {t = {30\quad\min}} \right)}} \right)}$

A high creep viscosity value (η_(creep)) at low stress, with a creeptime of 10 minutes (near zero shear rate), provides for a longer wear ofthe composition. Therefore, a lip composition with a high creepviscosity value (η_(creep)) at low stress will maintain its structure,thus its stability, at rest, will show less migration, and will providea lasting shine.

The creep viscosity (η_(creep)) of compositions in accordance with thepresent invention, at a constant stress (σ) of 0.8 Pa, is in the rangeof from 2 Pa.s to 150,000 Pa.s at 25° C.

The present invention is further described in terms of the followingnon-limiting example. Unless otherwise indicated, all parts andpercentages are on a weight-by-weight percentage basis.

EXAMPLE 1

A lip gloss composition in accordance with the present invention wasprepared per the following formula:

All values are expressed in % w/w. PHASE TRADE NAME % w/w A FINSOLV TN ¹25.43 B KRATON G1657 M 8.00 C REGALITE R1100 24.00 D PRISORINE 3631 ²10.00 CRODAMOL STS 24.26 E TITANIUM DIOXIDE 0.15 IRON OXIDE 0.13 D&C REDNO. 7 0.10 BLUE 1 LAKE 0.01 BLACK IRON OXIDE 0.04 FINSOLV TN ¹ 0.88 FMICA 3.00 AMIHOPE LL ³ 1.00 AEROSIL R972 3.00 TOTAL 100.00¹ C12-15 alkyl benzoate available from Finetex.² Pentaerythrityl tetraisostearate available from Uniqema.³ Lauroyl Lysine powder available from Ajinomoto.

Example 1 was prepared as follows:

The oil of phase A was pre-heated to 100° C. for 10 minutes, with mediummixing, using a propeller mixer.

Phase B (KRATON G1675 M) was added to phase A at 100° C.

Phase B and phase A were mixed at high speed for 30 minutes until phaseB was totally dissolved into phase A.

Phase C (Regalite R1100) was then slowly added into phase (A+B) withmedium mixing at 95° C. until the solution became homogeneous.

The temperature was reduced to 90° C. and phase D containing oilmixtures was added to phase (A+B+C), and mixed at low speed.

In a separate beaker Phase E ingredients were mixed, by hand, until thepigments were totally wet with oil to form a pigment mixture.

The pigment mixture was then transferred to a three-roll mill and milleduntil the colors became homogeneous to form a milled pigment mixture.

The milled pigment mixture was then transferred into a beaker containingphase (A+B+C+D) and mixed, at average speed, for approximately 5minutes.

Phase F was then slowly added into the beaker and mixed for 10 minutesat high speed.

Mixing speed was then reduced and the resulting fluid transferred intoindividual packages at 90° C.

The samples contained in the packages were then cooled to roomtemperature.

The samples exhibited desirable shine and wear properties.

Rheology of Example 1

The elastic/storage modulus G′, at a frequency of 0.01 rad/s, at atemperature of 25° C., was 26.5 Pa, for the formulation of example 1.

The creep viscosity, at a constant stress of 0.8 Pa, at a temperature of25° C., was 5.43×10³ Pa·s, for the formulation of example 1.

1. A cosmetic composition comprising: (a) at least one block copolymerhaving at least one hard segment and at least one soft segment; (b) atleast one tackifier component; (c) at least one solvent capable ofsolubilizing the at least one hard segment; (d) optionally, at least onecolorant; and wherein the at least one hard segment has a T_(g) value of50° C. or more, and the at least one soft segment has a T_(g) value of20° C. or less.
 2. The composition of claim 1 wherein (a) is a tri-blockthermoplastic elastomer of an A-B-A type copolymer wherein A correspondsto styrene and B corresponds to rubber.
 3. The composition of claim 1wherein (a) is a di-block thermoplastic elastomer of an A-B typecopolymer wherein A corresponds to styrene and B corresponds to rubber.4. The composition of claim 1 wherein (a) is a mixture of: (i) at leastone di-block thermoplastic elastomer of an A-B type copolymer and (ii)at least one tri-block thermoplastic elastomer of an A-B-A typecopolymer, wherein A corresponds to styrene and B corresponds to rubber.5. The composition of claim 1 wherein (a) has a styrene content of lessthan about 30% by weight, based on the weight of (a).
 6. The compositionof claim 1 wherein (a) is present in the composition in an amount offrom greater than 0% to about 50% by weight, based on the weight of thecomposition.
 7. The composition of claim 1 wherein (a) is present in thecomposition in an amount of from greater than 0% to about 10% by weight,based on the weight of the composition.
 8. The composition of claim 1wherein the at least one tackifier component is present in thecomposition in an amount of from greater than 0% to about 90% by weight,based on the weight of the composition.
 9. The composition of claim 1wherein the at least one tackifier component is present in thecomposition in an amount of from greater than 0% to about 30% by weight,based on the weight of the composition.
 10. The composition of claim 1wherein the at least one tackifier is a hydrogenated styrene/methylstyrene/indene copolymer.
 11. The composition of claim 1 wherein thetackifier has a solubility parameter corresponding to δ and the blockcopolymer has at least one segment with a solubility parametercorresponding to δ±2.
 12. The composition of claim 1 wherein the atleast one solvent capable of solubilizing the at least one hard segmenthas a viscosity of from about 1 to about 200 cps at room temperature.13. The composition of claim 1 wherein the at least one solvent capableof solubilizing the at least one hard segment has a viscosity of fromabout 2 to about 50 cps at room temperature.
 14. The composition ofclaim 1 wherein the at least one solvent capable of solubilizing the atleast one hard segment has a solubility parameter corresponding to δ′and the block copolymer has at least one hard segment with a solubilityparameter corresponding to δ′±2.
 15. The composition of claim 1 whereinthe at least one solvent capable of solubilizing the at least one hardsegment has a solubility parameter corresponding to δ′ and the blockcopolymer has at least one hard segment with a solubility parametercorresponding to δ′±0.7.
 16. The composition of claim 1 wherein the atleast one solvent capable of solubilizing the at least one hard segmenthas a weight average molecular weight of from about 100 to about 500.17. The composition of claim 1 wherein the at least one solvent capableof solubilizing the at least one hard segment further comprises at leastone co-solvent having a weight average molecular weight of from about500 to about
 2500. 18. The composition of claim 1 wherein the at leastone solvent capable of solubilizing the at least one hard segment ispresent in the composition in an amount of from greater than 0% to about85% by weight, based on the weight of the composition.
 19. Thecomposition of claim 17 wherein the co-solvent is present in thecomposition in an amount of from greater than 0% by weight to about 60%by weight, based on the weight of the composition.
 20. The compositionof claim 1 wherein the at least one solvent capable of solubilizing theat least one hard segment is chosen from linear or branched monoesters,diesters, triesters, and mixtures thereof.
 21. The composition of claim1 wherein the colorant is present in an amount effective to impart colorwhen applied onto lips.
 22. A process for treating lips comprisingcontacting the lips with the composition of claim
 1. 23. A cosmeticcomposition comprising: (a) from about 1 to about 10% by weight of atri-block thermoplastic elastomer of an A-B-A type copolymer wherein Acorresponds to styrene and B corresponds to rubber; (b) from about 1 toabout 40% by weight of at least one hydrogenated hydrocarbon resinderived from styrene/methyl styrene/indene copolymers; (c) from about 1to about 60% by weight of at least one ester of a weight averagemolecular weight of 100 to 500; and (d) optionally, at least onecolorant; all weights being based on the weight of the composition. 24.The composition of claim 1 wherein the composition has anelastic/storage modulus G′, at a frequency ω of 0.01 rad/s, ranging fromabout 0.01 Pa to about 500 Pa at 25° C.
 25. The composition of claim 23wherein the composition has an elastic/storage modulus G′, at afrequency ω of 0.01 rad/s, ranging from about 0.01 Pa to about 500 Pa at25° C.
 26. The composition of claim 1, wherein the composition has acreep viscosity (η_(creep)) ranging from about 2 Pa·s to about 150,000Pa·s, at 25° C.
 27. The composition of claim 23, wherein the compositionhas a creep viscosity (η_(creep)) ranging from about 2 Pa·s to about150,000 Pa·s, at 25° C.